(dihydroxy- and dicarbethoxy-phenyl) phenylcarboxamide compounds



United States Patent 3,329,700 (DIHYDROXY- AND DICARBETHOXY-PHENYL) PHENYLCARBOXAMIDE COMPOUNDS Milton Green, Newton Center, Mass., assignor to Polaroid Corporation, Cambridge, Mass., a corporation of Delaware No Drawing. Original application Feb. 15, 1962, Ser. No. 173,349, now Patent No. 3,262,924. Divided and this application Dec. 1, 1965, Ser. No. 510,969

5 Claims. (Cl. 260-463) This application is a division of application Ser. No. 173,349, filed Feb. 15, 1962, and now US. Patent No. 3,262,924, which in turn, is in part a continuation of application Ser. No. 703,515, filed Dec. 18, 1957, and now abandoned.

This invention relates to chemistry and, more particularly, to novel chemical compounds which are useful in preparing monochromatic and multichromatic photographic images.

U.S. Patent No. 2,983,606, issued on May 9, 1961 to Howard G. Rogers, discloses dilfusion transfer processes wherein a photographic negative material such as a photographic element comprising an exposed silver halide emulsion layer containing a latent image, is processed using a compound which is both a dye and a silver halide developer and designated as a dye developer, thereby imparting to the image-receiving element a reversed or positive dye image. In carrying out the process of this patent, a photosensitive element containing a silver halide emulsion is exposed and permeated with a liquid processing composition, for example, by immersing, coating, spraying, flowing, etc., in the dark, and the thus permeated exposed photosensitive element is brought into superposed relationship with an image-receiving layer. In a preferred embodiment, the photosensitive element contains a layer of dye developer and the liquid processing composition permeating the photosensitive element provides a solution of dye developer substantially uniformly distributed therein. As the exposed silver halide emulsion is developed, the oxidation product of the dye developer is immobilized or precipitated, in situ, with the developed silver, thereby providing an imagewise distribution of unoxidized dye developer dissolved in the liquid processing composition. At least part of the imagewise distribution of unoxidized dye developer is transferred, by imbibition, to the superposed image-receiving layer or element to form the .dye transfer image. While the dye developer may be utilized in the photosensitive element, for example, in, on, or behind the silver halide emulsion, it may also be utilized in the image-receiving element or in the liquid processing composition.

The present invention relates to novel dye developers which are particularly useful in photographic processes, products and compositions, such as described above and disclosed with more particularity in the aforementioned U.S. Patent No. 2,983,606.

One object of this invention, therefore, is to provide novel chemical compounds and novel syntheses for preparing these novel compounds.

Another object of the invention is to provide novel chemical compounds useful in photographic products, processes and compositions in which color developing agents are used to develop a latent image.

Yet another object of the invention is to provide novel chemical compounds useful in preparing monochromatic and multichromatic photographic images.

Other objects of the invention will in part be obvious and will in part appear hereinafter.

The invention accordingly comprises the product possessing the features, properties and the relation of components which are exemplified in the following detailed "Ice disclosure, and the scope of the application of which will be indicated in the claims.

For a further understanding of the nature and objects of the invention, reference should be had to the following detailed description.

The novel compounds of this invention are azo dye developers, that is, azo dyes containing at least one and not more than two silver halide developing functions, or derivatives thereof having a protected developing function, that is, one or two aromatic groups which upon hydrolysis form a developing function. In other words, the novel compounds of this invention comprise an azo dye having at least one and not more than two substituent of the following formula:

wherein R is hydrogen or an alkyl group, preferably a lower alkyl group, such as for example, methyl, ethyl, etc.; and R and R may be the same or different or may be hydroxyl or acyloxy groups. The term acyloxy as used herein is meant to signify the grouping wherein represents the radical of an azo dye molecule wherein Z represents the azo dye molecule other than the amino group or groups; n is a positive integer from 1 to 2; and R, R and R have the meanings heretofore noted. The preferred compounds of this invention are also dye developers of the following formula:

3 wherein R, R and R have meanings previously noted; Y may be N=NQ, or a pyrazolone dye radical linked to the phenylene radical of said vention, mention may be made of the following compounds:

H l i H I OH 4- (4-[p-(2 ,5 '-dihydroxypheuyl) -pheuylcarboxamido]- phenylazo) -3-rnethyl-1-phenyl-5-pyrazolone 4- (4'- [p- (2' ',5 '-bis-ca.thyloxypheny1) -pheuylcarbxamido]- phenylazo 3-methyl1-phenyl-5-pyrazolone I OCH;

2- (H- [p- 2 ,5 -dihydroxyphenyl) -phenylcarboxamido phenylazo -4-methoxy-1-naphth01 2- y- [p- 2' ,5 '-bis-cathyloxyphenyl -pheny1carboxamido phenylazo) -4-methoxy-Lnaphthol 3-carbethoxy4- (4- [m- 2 ,5 -dihy droxyphenyl) -phenylcarboxamldo1phenylazo) -1-phenyl-5-pyrazolone The compounds of this invention containing an amino or substituted amino group may also be present in the form of acid addition salts such as, for example, the hydrochloride.

One method of preparing the novel compounds of this invention comprises reacting, in the presence of a suitable halogen acid acceptor such as, for example, quinoline, anhydrous pyridine, etc., a compound of the formula:

(D) acylloxy u C-halogen aeyloxy D with a compound of the formula:

N -ArX wherein R has the same significance as previously noted; Ar is an arylene nucleus, i.e., phenylene; and X is a group convertible to a primary amino group subsequent to reaction such as, for example, a nitro group. The resulting primary amine may be diazotized and coupled according to conventional methods to provide suitable compounds within the scope of this invention.

After reaction and prior to use as a photographic dye developer, the respective acyloxy groups may be removed by deesterification such as for example, by hydrolysis in the presence of alkali to form the hydroquinonyl developing function.

However, it is to be noted that where desired the respective acyloxy groups of the aforementioned intermediate products, which may be represented by the formula:

(F) alcyloxy II I CNAr-X l acyloxy wherein Ar and R have the meanings heretofore given and X is a nitro or a primary amino group; may also be 5 removed by deesterification and the resulting dihydroxyphenyl products thereof may then be utilized as photo graphic developing agents.

As examples of compounds contemplated within the scope of Formula (F) and the free hydroquinonyl forms thereof, mention may be made of:

7 OH a I OH 4- (p- [2,5 -bis-ca.thylxyphenyl] -phenylcarboxamido) -anlline 4- (p- 2,5'-dihydroxyphenyl] -pheny1carboxamido nitrobenzene O-C-O CzH;

Example 1 To a hot solution of 7 g. of p-carboxyphenylquinone, prepared according to the procedure of Kvalnes in JACS 56, 2478 (1934), in 350 cc. of 95% ethanol is added a solution of 10 g. of sodium hyposulfite in 40 cc. of water. The original amber color discharges, and a white precipitate forms which is removed by filtration. The filtrate is acidified with 10 cc. of concentrated hydrochloride acid and a white precipitate forms which is removed by filtration. The resultant filtrate is then evaporated to dryness and the residual solid yellow residue crystallized from 250 cc. of water containing a trace of ethanol after clarification with charcoal. The resultant product, 2.5 g. of a white solid, p-(2,5-dihydroxyphenyl)-benzoic acid, exhibits an M.P. at 222 C. Concentration of the mother liquor to 50 cc. results in an additional yield of 0.3. g. of the desired product exhibiting an M.P. at 218 C.

A solution of 2.16 g. of sodium hydroxide in 40 cc. of water is deaerated with nitrogen for 10 minutes. 3.1 g. of p-(2,5-dihydroxyphenyl)-benzoic acid is added to the solution and the mixture chilled for 10 minutes. To the chilled mixture, 5.1 cc. of ethyl chloroformate is added portionwise over an interval of 30 minutes. The resultant mixture is stirred for 30 minutes during which time a white solid precipitates. The mixture is then acidified with 11 cc. of 3 N hydrochloric acid, casuing a gum to separate. Contact of the gum with small amounts of aqueous ethanol results in solidification. The solid product is crystallized from aqueous ethanol and then recrystallized from a benzene-hexane mixture yielding 2.5 g. of a White solid, p- (2,5-bis-cathyloxyphenyl)-benzoic acid, exhibiting an M.P. at 174 to 175 C.

Analysis of this product.Calculated as C I-1 0 C, 61.0%; H, 4.8%. Found: C, 61.2; H, 5.0%.

2.5 g. of p-(2,5-bis-cathyloxyphenyl)-benzoic acid are refluxed with 10 cc. of thionyl chloride for 2.5 hours. Excess thionyl chloride is evaporated in vacuo and the residual oil mixed with benzene. The benzene is then evaporated and the residual oil further purified by a second benzene treatment. The resultant product, an oil, p- (2,5-bis-cathyloxyphenyl)-benzoyl chloride, may be utilized in the subsequent reaction without further purification.

To the above product, 0.94 g. of p-nitroaniline and 0.55 cc. of pyridine in 20 cc. of benzene are added and the mixture refluxed for 1 hour. The mixture is then cooled, extracted with water and the organic layer separated, dried over magnesium sulfate and filtered into 150 cc. of hexane. An orange gum separates which solidifies upon standing overnight and is crystallized from 25 cc. of ethanol yielding 2.5 g. of a white solid, 4-(p-[2',5'-bis-cathyloxyphenyl]-phenylcarboxamido) nitrobenzene (Formula 10), melting at 138 to 139 C.

Where desired the product of the above reaction may be deesterified, for example, by hydrolysis in the presence of alkali, to yield, 4-(p-[2',5-dihydroxyphenyl]-phenylcarboxamido) -nitrobenzene, (Formula 9).

A mixture of 2.5 g. of 4-(p-[2',5'-bis-cathyloxyphenyl]- phenylcarboxamido)-nitrobenzene (Formula 10), cc. of ethanol and 5 g. of 7% palladium/barium sulfate catalyst is hydrogenated at 30 p.s.i. of hydrogen. Theoretical uptake occurs in 1 hour. The catalyst is removed by filtration and the filtrate evaporated to dryness. Triturating the residual oil with 20 cc. of cold 1:1 hydrochloric acid yields a white solid product which is recrystallized from 40 cc. of ethanol yielding 1.7 g. of a white amorphous solid, 4-(p-[2',5'-bis-cathyloxyphenyl] phenylcarboxamido)-aniline hydrochloride (the hydrochloride acid addition salt of Formula 8), which decomposes at 203 C.

Where desired the product of the above reaction may be deesterified, such as for example, by hydrolysis in the presence of alkali, to yield 4-(p-[2,5'-dihydroxyphenyl]- phenyl-carboxamido)-aniline (Formula 7).

Example 2 1.7 g. (.00344 mol) of 4-(p-[2,5'-bis-cathyloxyphenyIJphenylcarboxamido)-aniline hydrochloride (the hydrochloride acid addition salt of Formula 8 as prepared in Example 1), are dissolved in a warm solution of 20 cc. of glacial acetic acid and 0.27 cc. (.00344 mol) of 12.5 N hydrochloric acid. The solution is cooled, diazotized at 10 C. with sodium nitrite and poured into a 50 cc. icewarm mixture. The mixture is then added, over a 30 minute interval, to a mixture of 0.59 g. (.0034 mol) of 3- methyl-l-phenyl-5-pyrazolone, 50 cc. of acetone and 10 cc. of pyridine. 245 cc. of 10% sodium carbonate solution are added portionwise concurrently with the diazo solution to maintain a pH of 7 to 8. The resultant orangered slurry is stirred for 1 hour, filtered and the filter cake washed with Water yielding 1.7 g. (dry Weight) of 4-(4'- [p-(2",5" bis cathyloxyphenyl)-phenylcaboxamido]- phenylazo)-3-methyl-l-phenyl-S-pyrazolone (Formula 2).

Example 3 1.7 g. of 4-(4-[p-(2",5-bis-cathyloxyphenyl)-phenylcarboxamido]-phenylazo) 3 methyl-l-phenyl-S-pyrazolone (Formula 2 as prepared in Example 2), are treated in vacuo with a mixture of 2 g. of potassium hydroxide, 30 cc. of ethanol and 10 cc. of water with intermittent warming on a steam bath for 3 minutes. The product is precipitated with a dilute hydrochloric acid solution, the resultant slurry filtered and the filter cake washed with water. The dye is further purified by dissolving it in a Methylcellosolve solution, precipitating with a 1% hydrochloric acid solution and washing with hot water. A yield of 0.9 g. (dry weight) of 4-(4- [p-(2,5"-dihydroxyphenyl)-phenylcarboxamido]phenylazo) 3 methyl-1- phenyl-S-pyrazolone (Formula 1), is obtained which decomposes at 258 to 260 C. The spectral absorption curve of this product exhibits a k at 425 m in ethanol; e=33,000.

Since certain changes may be made in the above product without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

What is claimed is:

1. A compound of the formula:

Ill]

' 8 wherein:

R is a member of the group consisting of hydrogen and lower alkyl; X is a member of the group consisting of nitro and primary amino; Ar is phenylene; and R and R each are selected from the group consisting of hydroxy and cathyloxy. 2. 4-(p-[2',5-dihydroxyphenyl] phenylcarboxamido)- aniline.

3. 4 (p [2,5' bis cathyloxyphenyl]-phenyl-carboxamido)-aniline.

4. 4-(p-[2',5'-dihydroxyphenyl] pheny1carboxamido)- nitrobenzene.

5. 4 (p [2,5' bis cathyloxyphenyl]-pheny1carboxamido)-nitrobenzene.

References Cited UNITED STATES PATENTS 3,214,469 10/1965 Green et a1 260-463 XR CHARLES B. PARKER, Primary Examiner.

FLOYD D. HIGEL. Assistant Examiner. 

1. A COMPOUND OF THE FORMULA: 